Macrocyclic oligomers containing spiro(bis)indane moieties

ABSTRACT

Macrocyclic oligomers, including polycarbonates, polyesters, polyamides, polyimides, polyetherketones and polyethersulfones, are conveniently prepared from various spiro(bis)indane compounds, especially the 6,6&#39;-difunctional 3,3&#39;,3&#39;-tetramethylspiro(bis)indanes. The macrocyclic oligomers may be conveniently converted to linear polymers.

This applicatation is a continuation-in-part of the following copendingapplications:

Ser. No. 887,503, filed July 21, 1986, now U.S. Pat. No. 4,736,016;

Ser. No. 920,540, filed Oct. 20, 1986, now U.S. Pat. No. 4,757,132;

Ser. No. 20,264, filed Feb. 27, 1987, now U.S. Pat. No. 4,808,754;

Ser. No. 26,517, filed Mar. 17, 1987, now U.S. Pat. No. 4,789,725; and

Ser. No. 64,650, filed June 22, 1987, now U.S. Pat. No. 4,837,298.

This invention relates to macrocyclic oligomers, and more particularlyto their preparation from compounds uniquely capable of conversionthereto.

U.S. Pat. Nos. 4,644,053 and 4,696,998 disclose cyclic polycarbonateoligomers and cyclic heterocarbonates, which are capable of conversionto high molecular weight linear homo- and copolycarbonates underreactive processing conditions. Cyclic polyarylates of similar molecularstructure are disclosed in the aforementioned copending application Ser.No. 920,540. While cyclic materials of this kind are often capable offormation from a wide variety of organic dihydroxy compounds, yields areoften low because the geometries of said organic dihydroxy compounds arenot favorable for cyclization, preferring the formation of linearpolymers.

The present invention is based on the discovery that compoundscontaining spirobiindane moieties are uniquely and generically capableof forming a broad spectrum of macrocyclic oligomers, often inpreference to linear polymers. It is possible, however, to convert saidoligomers by relatively simple means to linear polymers having a widescope of utilities.

As broadly defined, therefore, the invention includes compositionscomprising random macrocyclic monomer and oligomer compoundscorresponding to the formula ##STR1## wherein the Z¹ radicals areidentical linking groups; A¹ is a spiro(bis)indane moiety of the formula##STR2## about 60% of the R¹ groups are divalent aromatic organicradicals and the balance thereof are divalent aliphatic, alicyclic oraromatic organic radicals; each R² is independently C₁₋₄ primary orsecondary alkyl or halo; a is from 1 to about 12, b is from 0 to 90% oftotal --A--Z--and --R¹ --Z¹ --moieties and n is 0-3.

As used herein, the term "macrocyclic oligomer" denotes compounds inwhich the spiro(bis)indane groups are part of a larger ring structure.Thus, the mere fact that the A¹ moiety is itself cyclic is notsignificant to the macrocyclic nature of the compound; rather, thepresence of a larger ring structure is mandatory.

The spiro(bis)indane units of formula II are obviously derived from6,6'-difunctional 3,3,3',3'-tetramethylspiro(bis)indanes (hereinaftersometimes simply "spirobiindanes"), which may be substituted orunsubstituted. The R² values therein may be alkyl radicals such asmethyl, ethyl, 1-propyl or 2-propyl, or halo atoms such as chloro orbromo. Among compounds containing such R² values, methyl and chloro arepreferred; however, the most preferred compounds are the6,6'-difunctional 3,3,3',3'-tetramethylspiro(bis)indanes, in which n is0.

The compositions of the invention include macrocyclic monomerscontaining only one--A¹ --Z¹ --moiety. Most often, however, saidcompositions are mixtures of oligomers containing at least two of saidmoieties. The linking Z¹ moieties, all of which are identical, areusually ether, ester, amide, imide or amic acid precursor thereof, orcarbonate moieties or larger organic groups containing such moieties.

The R¹ values, if present, may be different but are usually the same. Ingeneral, the tendency to form macrocyclic oligomers decreases with anincrease in the proportion of--R¹ --Z¹ --moieties in the molecule. Saidproportion, as a percentage of the number of total moieties present, ismost often about 10-90% and preferably up to about 50%.

At least about 60% of the total number of R¹ values are aromatic and thebalance may be aliphatic, alicyclic, aromatic or mixed; those which arealiphatic or alicyclic generally contain up to about 8 carbon atoms. The.[.R² .]. .Iadd.R¹ .Iaddend.values may contain substituents such ashalo, nitro, alkoxy, lactone and the like. Most often, however, all R¹radicals are hydrocarbon radicals.

Preferably at least about 80% of the total number of R¹ values in themacrocyclic oligomer compositions, and most desirably all of said R¹values, are aromatic. The aromatic R¹ radicals preferably have theformula

    --A.sup.2 --Y.sup.1 --A.sup.3 --                           (III)

wherein each of A² and A³ is a monocyclic divalent aromatic radical andY¹ is a bridging radical in which one or two atoms separate A¹ from A².The free valence bonds in formula III are usually in the meta or parapositions of A² and A³ in relation to Y¹.

In formula III, the A² and A³ values may be unsubstituted phenylene orsubstituted derivatives thereof, illustrative substituents (one or more)being alkyl, alkenyl, halo (especially chloro and/or bromo), nitro,alkoxy and the like. Unsubstituted phenylene radicals are preferred.Both A² and A³ are preferably p-phenylene, although both may be o- orm-phenylene or one o- or m-phenylene and the other p-phenylene.

The bridging radical, Y¹, is one in which one or two atoms, preferablyone, separate A² from A³. It is most often a hydrocarbon radical andparticularly a saturated radical such as methylene, cyclohexylmethylene,2-[2.2.1]-bicycloheptylmethylene, ethylene, isopropylidene,neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylideneor adamantylidene, especially a gem-alkylene (alkylidene) radical. Alsoincluded, however, are unsaturated radicals and radicals which containatoms other than carbon and hydrogen; for example,2,2-dichloroethylidene, carbonyl, phthalidylidene, oxy, thio, sulfoxyand sulfone.

The copolymeric compositions of this invention are random copolymers;that is, the distribution of the--A¹ --Z¹ --and--R¹ --Z¹ --moieties ineach molecule is random. In this sense, formula I is only a stylizedstructural formula since it suggests a block copolymer structure whichis not contemplated.

In its broadest sense, therefore, the invention includes a wide varietyof macrocyclic oligomers containing spirobiindane moieties. Oligomerscontaining the following structural units are illustrative; in thesestructures, A¹ represents the spirobiindane moiety of formula II.

Polycarbonate: ##STR3##

Polyester: ##STR4## wherein R³ is a divalent aliphatic or m- or p-linkedmonocyclic aromatic or alicyclic radical.

Polyamide--includes the following: ##STR5## wherein:

R⁴ is a substituted or unsubstituted C₂₋₄ alkylene, m-phenylene orp-phenylene radical;

R⁵ is a substituted or unsubstituted alkylene radical or arylene radicalother than o-arylene; and

p is 0 or 1; and ##STR6## wherein A⁴ is a monocyclic or bicyclic m- orp-linked arylene radical or ##STR7## R⁶ is C₁₋₄ primary or secondaryalkyl, phenyl or substituted phenyl and R³ is as previously defined.

Polyimide and polyamideimide (and polyamic acid precursors thereof) -includes the following: ##STR8## wherein:

Z² is a single bond, a divalent aliphatic or alicyclic radicalcontaining about 1-12 carbon atoms, --O--, --CO--, --S--, --SO₂ --,--O-Q-O--, --SO₂ -Q-SO₂ --, ##STR9##

Q is a divalent aliphatic or aromatic radical; and R⁴, R⁶ and p are aspreviously defined; and ##STR10## wherein Z³ is R³ or --R⁴ --Z⁴ --R⁴--or has formula VIII, Z⁴ is ##STR11## and R³ and R⁴ are previouslydefined.

Polyetherketone and polyethersulfone:

    --O--A.sup.1 --O--A.sup.5 --                               (XI)

wherein A⁵ is an aromatic radical containing at least one --CO--or.[.--SO₂ .]. .Iadd.--SO₂ --.Iaddend.group.

Consideration will now be given to each of these types of oligomers indetail, with preferred parameters and illustrative methods ofpreparation.

Polycarbonates

Macrocyclic polycarbonate oligomer compositions corresponding to formulaIV, and corresponding copolycarbonates, may be prepared by contacting acomposition comprising at least one compound of the formula

    Y.sup.2 0--A.sup.1 --OY.sup.2                              (XII)

or a mixture thereof with at least one compound of the formula

    Y.sup.3 O--R.sup.2 --OY.sup.3                              (XIII)

wherein R² is as previously defined, the Y² and Y³ values in eachcompound are both H or ##STR12## and X¹ is chlorine or bromine, at leastabout 75% of the total number of Y² and Y³ moieties being ##STR13## withat least one oleophilic aliphatic or heterocyclic tertiary amine and anaqueous alkali or alkaline earth metal hydroxide or carbonate solution(hereinafter sometimes "base"), in a substantially non-polar organicliquid which forms a two-phase system with water. The details ofpreparation are similar to those for preparing cyclic polycarbonateoligomer mixtures as described in the aforementioned U.S. Pat. No.4,644,053, the disclosure of which is incorporated by reference herein.

It will be apparent from the foregoing that at least one of thecompounds of formulas XII and XIII must be a bishaloformate. While theX¹ values therein may be chlorine or bromine, the bischloroformates, inwhich X¹ is chlorine, are most readily available and their use istherefore preferred. Reference to bischloroformates hereinafter willfrequently include all compounds of formulas XII and XIII when thecontext permits. It should be understood, however, that otherbishaloformates may be substituted for the bischloroformates asappropriate.

The bischloroformates comprise a major proportion of the compounds offormulas XII and XIII, at least about 60%, preferably at least about 75%and most preferably at least about 90% of the total number of Y² and Y³moieties being chloroformate moieties. Any remaining compounds offormulas XII and XIII are dihydroxy compounds, preferably bisphenols.

When the compound of formula XII is free6,6'-dihydroxy-3,3,3',3'-tetramethylspiro(bis)indane (hereinafter SBI),it may be necessary to employ a minor proportion of a solvent therefor,such as tetrahydrofuran, to ensure its dissolution in the reactionmixture. Most often, however, bischloroformates alone are used.

The proportions of compounds of formulas XII and XIII in the reactionmixture will depend on whether the cyclic composition being prepared isa homopolycarbonate (whereupon only the compound of formula XII will beused) or a copolycarbonate. The copolycarbonates generally comprise atleast about 10 mole percent of units of formula IV, and thereforerequire at least about 10 mole percent of the compound of formula XII inthe reaction mixture, the balance having formula XIII.

Any bischloroformates may be employed in substantially pure, isolatedform. For this purpose, it is possible to prepare SBI bischloroformateby a variation of the method described in Example 4 of British Pat.613,280, substituting diethylaniline for the dimethylaniline recitedtherein.

It is frequently preferred, however, to use one or more crudebischloroformate products. Suitable crude products may be prepared byany known methods for bischloroformate preparation. Typically, at leastone bisphenol (and, for the preparation of copolycarbonates, a mixtureof bisphenols such as those of bisphenol A and SBI) is reacted withphosgene in the presence of a substantially inert organic liquid, asdisclosed in the following United States patents:

    ______________________________________                                               3,255,230     3,966,785                                                       3,312,661     3,974,126.                                               ______________________________________                                    

The disclosures of these patents are incorporated by reference herein.

In addition to the bisphenol bischloroformate, such crudebischloroformate products may contain oligomer bischloroformates. Mostoften, a major proportion of the crude product comprises monomer, dimerand trimer bischloroformate. Higher oligomer bischloroformates, andmonochloroformates corresponding to any of the aforementionedbischloroformates, may also be present, preferably only in relativelysmall amounts.

More preferably, the preparation of the crude bischloroformate producttakes place in the presence of aqueous alkali. The pH of the reactionmixture may be up to about 12. It is generally found, however, that theproportion of high polymer in the cyclic oligomer mixture is minimizedby employing a crude bischloroformate product comprising a major amountof bisphenol bischloroformate and only minor amounts of any oligomerbischloroformates. Such products may be obtained by a variant of themethod disclosed in U.S. Pat. No. 4,638,077, the disclosure of which isalso incorporated reference herein.

In that method, phosgene is passed into a mixture of a substantiallyinert organic liquid and a bisphenol, said mixture being maintained at atemperature within the range of about 10-40° C., the phosgene flow ratebeing at least 0.15 equivalent per equivalent of bisphenol per minutewhen the temperature is above 30° C. An aqueous alkali metal or alkalineearth metal base solution is simultaneously introduced as necessary tomaintain the pH in the range of about 0.5-8.0. By this method, it ispossible to prepare bischloroformates of compounds such as bisphenol Ain high yield while using a relatively small proportion of phosgene,typically up to about 1.1 equivalent per equivalent of bisphenol.

For the preparation of SBI bischloroformate compositions, theabove-described method is not satisfactory since SBI swells and gels inwater-methylene chloride mixtures at low pH. The monochloroformate ofSBI is, however, apparently soluble in such mixtures (particularly inthe methylene chloride phase thereof).

Therefore, it is possible to prepare SBI bischloroformate compositons bypassing phosgene into a heterogeneous mixture of solid SBI, asubstantially inert organic liquid (e.g., methylene chloride) and anaqueous alkali metal or alkaline earth metal base solution, said mixturebeing maintained at a temperature within the range of about 10°-40° C.and at a pH of the aqueous phase in the range of about 8-14, until allsolids have dissolved, and then continuing phosgene passage as the pH isdecreased to a value in the range of 2-8, preferably 2-5. This method isdisclosed and claimed in copending, commonly owned application Ser. No.926,685, filed Nov. 4, 1986.

When one of these methods is employed, it is obvious that the crudebischloroformate product will ordinarily be obtained as a solution in asubstantially non-polar organic liquid such as those disclosedhereinafter. Depending on the method of preparation, it may be desirableto wash said solution with a dilute aqueous acidic solution to removetraces of base used in preparation.

The tertiary amines ("tertiary" in this context denoting the absence ofN--H bonds) generally comprise those which are oleophilic (i.e., whichare soluble in and highly active in organic media, especially those usedin the oligomer preparation method of this invention), and moreparticularly those which are useful for the formation of polycarbonates.Reference is made, for example, to the tertiary amines disclosed in U.S.Pat. Nos. 4,217,438 and 4,368,315, the disclosures of which areincorporated by reference herein. They include aliphatic amines such astriethylamine, tri-n-propylamine, diethyl-n-propylamine andtri-n-butylamine and highly nucleophilic heterocyclic amines such as4-dimethylaminopyridine (which, for the purposes of this invention,contains only one active amine group). The preferred amines are thosewhich dissolve preferentially in the organic phase of the reactionsystem; that is, for which the organic-aqueous partition coefficient isgreater than 1. This is true because intimate contact between the amineand the compounds of formulas XII and XIII is essential for theformation of the monocyclic oligomer composition. For the most part,such amines contain at least about 6 and preferably about 6-14 carbonatoms.

The most useful amines are trialkylamines containing no branching on thecarbon atoms in the 1- and 2-positions. Especially preferred aretri-n-alkylamines in which the alkyl groups contain up to about 4 carbonatoms. Triethylamine is most preferred by reason of its particularavailability, low cost, and effectiveness in the preparation of productscontaining low percentages of linear oligomers and high polymers.

Suitable aqueous alkali or alkaline earth metal hydroxide or carbonatesolutions include lithium, sodium, potassium and calcium hydroxide andsodium and potassium carbonate. Lithium, sodium or potassium hydroxideare most often used, with sodium hydroxide being preferred because ofits availability and relatively low cost. The concentration of thesolution is not critical and may be about 0.1-16 M, preferably about0.2-10 M.

The fourth essential component in the macrocyclic polycarbonate oligomerpreparation method is a substantially non-polar organic liquid whichforms a two-phase system with water. The identity of the liquid is notcritical, provided it possesses the stated properties. Illustrativeliquids are aromatic hydrocarbons such as toluene and xylene;substituted aromatic hydrocarbons such as chlorobenzene,o-dichlorobenzene and nitrobenzene; chlorinated aliphatic hydrocarbonssuch as chloroform and methylene chloride; and mixtures of the foregoingwith ethers such as tetrahydrofuran. Methylene chloride is generallypreferred.

To prepare the macrocyclic polycarbonate oligomer composition accordingto the above-described method, the reagents and components aremaintained in contact under conditions whereby the bischloroformates arepresent in low concentration. Actual high dilution conditions, requiringa large proportion of organic liquid, may be employed but are usuallynot preferred for cost and convenience reasons. Instead, simulated highdilution conditions known to those skilled in the art may be employed.For example, in one embodiment of the method the bischloroformates (andoptionally other reagents) are added gradually to a reaction vesselcontaining solvent.

Although addition of said bischloroformates neat (i.e., withoutsolvents) is within the scope of this embodiment, it is frequentlyinconvenient because many bischloroformates are solids. Therefore, theyare preferably added as a solution in a portion of the organic liquid,especially when they consist essentially of bischloroformate. Theproportion of organic liquid used for this purpose is not critical;about 25-75% by weight, and especially about 40-60%, is preferred.

The reaction temperature is generally in the range of about 0°-50° C. Itis most often about 0°-40° C. and preferably 20°-40° C.

For maximization of the yield and purity of macrocyclic polycarbonateoligomers as opposed to high polymer and insoluble and/or intractableby-products, it is preferred to use not more than about 1.5 mole ofbischloroformates, calculated as bisphenol bischloroformate, per literof organic liquid in the reaction system, including any liquid used todissolve said compounds. Preferably, about 0.003-1 0 mole of saidcompounds is used when it consists entirely of bischloroformate, and nomore than about 0.5 mole is used when it is a bisphenol-bischloroformatemixture. It should be noted that this is not a molar concentration inthe organic liquid when said compounds are added gradually, since theyare consumed as they are added to the reaction system.

The molar proportions of the reagents constitute another importantfeature for yield and purity maximization. The preferred molar ratio ofamine to compounds of formulas .[.XIV.]. .Iadd.XII .Iaddend.and .[.XV.]..Iadd.XIII .Iaddend.when said compounds consist essentially ofbischloroformates is about 0.1-1.0:1 and most often about 0.15-0.6:1,and that of base to said compounds is about 1.5-3:1 and most often about2-3:1. When a bischloroformate-bisphenol combination is used, thepreferred molar ratio for amine is about 0.1-0.5:1.

A highly preferred method for preparing the macrocyclic polycarbonateoligomer compositions of this invention comprises conducting thereaction using as the amine at least one aliphatic or heterocyclictertiary amine which, under the reaction conditions, dissolvespreferentially in the organic phase of the reaction system, andgradually adding the bischloroformates and at least a portion of theamine and base simultaneously to the organic liquid or to a mixturethereof with water, said liquid or mixture being maintained at atemperature in the range of about 0°-50° C.; the amount ofbischloroformates used being up to about 0.7 mole for each liter oforganic liquid present in the reaction system, and the total molarproportions of amine and base, respectively, to bischloroformates beingapproximately 0.06-2.0:1 and 2-3:1, respectively; and recovering thecyclic oligomers thus formed.

A factor of some importance in this embodiment is the concentration ofavailable amine, which should be maintained at a level as constant aspossible during the entire bischloroformate addition period. If all ofthe amine is present in the reaction vessel into which the amine isintroduced, its concentration steadily decreases, principally bydilution. On the other hand, if the amine is introduced continuously orin equal increments during introduction of bischloroformate, itsavailable concentration is initially low and increases more or lesssteadily during the addition period. These fluctuations can result in ahigh and constantly varying proportion of high polymer in the product.

It has been found advantageous to introduce the amine in one initiallarge portion, usually about 40-95% and preferably about 40-75% byweight of the total amount, followed by incremental or continuousaddition of the balance thereof. By this procedure, the concentration ofavailable amine is maintained at a fairly constant level in the organicphase during the entire addition period, and it is possible to minimizethe proportion of high polymer in the product. Typically, high polymercontent is 10% or less when this mode of addition is used.

Under these conditions, it is usually advantageous for the reactionvessel to initially contain about 5-40% and preferably about 5-30% oftotal base. The balance thereof is also introduced continuously orincrementally. As in the embodiment previously described, anotherportion of organic liquid may serve as a solvent for thebischloroformates.

Among the other principal advantages of this preferred embodiment arethe non-critically of the degree of dilution of the reagents and theability to complete the addition and reaction in a relatively shorttime, regardless of .[.reactions.]. .Iadd.reaction .Iaddend.scale. Itordinarily takes only about 25-30 minutes to complete cyclic oligomerpreparation by this method, and the cyclic oligomer yield may be 85-90%or more. By contrast, use of a less preferred embodiment may, dependingon reaction scale, require an addition period as long as 8-10 hours.

In this preferred embodiment, the pH of the reaction mixture istypically in the range of about 9-14 and preferably about 12. When thebischloroformates (and optionally the amine) are added to all of thebase, on the other hand, the initial pH remains on the order of 14during essentially the entire reaction period.

When the reaction has been completed, impurities may be removed in thenecessary amounts by conventional operations such as combining the crudeproduct, as a solid or in solution, with a .[.on-solvent.]..Iadd.non-solvent .Iaddend.for said impurities. Illustrativenon-solvents include esters such as methyl acetate and ethyl acetate.

Recovery of the macrocyclic polycarbonate oligomers normally meansmerely separating the same from diluent (by known methods such as vacuumevaporation) and, optionally, from high polymer and other impurities.The degree of sophistication of recovery will depend on such variablesas the intended end use of the product. Among the macrocycliccopolycarbonates contemplated as part of the invention are macrocyclicpolyphenylene ether-polycarbonates containing, in addition to thestructural units of formula IV, units corresponding to --R¹ --Z¹ --whichhave the formula ##STR14## wherein:

each Q¹ is independently halogen, primary or secondary lower alkyl(i.e., alkyl containing up to 7 carbon atoms), phenyl or hydrocarbonoxy;

each Q² is independently hydrogen, halogen, primary or secondary loweralkyl, phenyl or hydrocarbonoxy;

each R⁸ is independently C₁₋₈ primary or secondary alkyl, phenyl orhalo;

each R⁹ is independently hydrogen, methyl, ethyl or phenyl;

m is from 0 to 4;

x is from 1 to about 5; and

p is as previously defined.

The moieties of formula XIV therein may or may not contain a methyleneor substituted methylene bridge linking two of the aromatic rings(according as p is 1 or 0). The substituents on said bridge, if any, aremethyl, ethyl or phenyl, with methyl being preferred. Especiallypreferred are the compounds in which each R⁹ is methyl, m is 0 and p is1; that is, compounds derived from bisphenol A.

Also present in the moiety of formula XIV are from 1 to about 5, andpreferably from 1 to 3, phenylene ether units. Examples of suitableprimary lower alkyl groups suitable for Q¹ and Q² therein are methyl,ethyl, n-propyl, n-butyl, isobutyl, n-amyl, isoamyl, 2-methylbutyl,n-hexyl, 2,3-dimethylbutyl, 2-, 3- or 4-methylpentyl and thecorresponding heptyl groups. Examples of secondary lower alkyl groupsare isopropyl, sec-butyl and 3-pentyl. Preferably, any such alkylradicals are straight chain rather than branched. Most often, each Q¹ isalkyl or phenyl, especially C₁₋₄ alkyl and preferably methyl, and eachQ² is hydrogen.

The macrocyclic polyphenylene ether-polycarbonates may be prepared bythe above-described polycarbonate process, substituting for the compoundof formula XIII at least one oligomeric compound of the formula##STR15## wherein Q¹, Q², R⁸, R⁹, Y³, m and p are as definedhereinabove, and otherwise varying the process as described hereinafter.

The oligomeric compounds of formula XV are polyphenylene ether-derivedbisphenols and their bishaloformate derivatives. They may be prepared byequilibration of a polyphenylene ether with a bisphenol of the formula##STR16## in the presence of a phenoxy radical which may be generated bya diphenoquinone. A bisphenol containing no more than about 5polyphenylene ether units is desired, and it may be produced byemploying a ratio of moles of bisphenol to units in the polyphenyleneether of at least about 0.1:1 and preferably about 0.1-1.0:1. Thismethod of preparing polyphenylene ether-derived bisphenols is disclosed,for example, in U.S. Pat. No. 3,496,236, the disclosure of which is alsoincorporated by reference herein.

The molar ratio of the compound of formula XII to that of formula XIV isgenerally about 5-10:1, and preferably about 7-8:1. The concentration ofthe base solution is most desirably no higher than about 5 M.

In a preferred embodiment of the preparation method, the compounds offormulas XII and XIV, or a combination thereof with the amine, are addedgradually to a mixture of the other materials. It is within the scope ofthis embodiment to incorporate the amine in the mixture to which saidcompounds are added, or to add it gradually, either in admixture withsaid compounds or separately. Continuous or incremental addition ofamine is frequently preferred. The reaction temperature is preferablyabout 40°-50° C.

For maximization of the yield and purity of macrocyclic polyphenyleneether-polycarbonate oligomers, it is preferred to use up to about 0.7mole and preferably about 0.1-0.6 mole of compounds of formulas XII andXIV per liter of organic liquid in the reaction system, including anyliquid used to dissolve said compounds. The preferred molar ratio ofamine to said compounds is about 0.05-1.5:1. and most often about0.1-1.0:1. The molar ratio of base to said compounds is usually about1-5:1.

Polyesters

The A⁵ value in formula V may be a divalent aliphatic, alicyclic oraromatic radical. Suitable aromatic radicals are similar to A² and A³,with the proviso that they are m- or p-linked. The alicyclic radicalsare similarly linked and most often contain about 4-8 carbon atoms.

The R³ may be considered as being derived from a dicarboxylic acid ofthe formula R³ (COOH)₂. Thus, suitable dicarboxylic acids includeadipic, pimelic and cyclohexane-1,3-dicarboxylic acids and theunsubstituted and substituted terephthalic, isophthalic andpyridine-2,6-dicarboxylic acids. The unsubstituted aromatic acids,especially isophthalic and terephthalic and most especially isophthalicacid, are preferred.

The macrocyclic polyester oligomers generally comprise mixtures ofoligomers, principally having degrees of polymerization up to about 7.The predominant oligomer is usually the trimer.

Such oligomers may be prepared by adding a dicarboxylic acid chloride ofthe formula R³ (COCl)₂ to a mixture of an organic liquid as describedhereinabove and a salt of the spirobiindane bisphenol, the latter beingmaintained in low concentration. It is often preferred to employ adi-(alkali metal) salt in a mixed aqueous-organic medium. Also presentis a catalyst comprising at least one tertiary amine or quaternaryammonium salt, generally in the amount of about 0.1-15.0 mole percentbased on spirobiindane bisphenol.

For the preparation of macrocyclic copolyesters, there may also beemployed at least one second salt of a dihydroxy compound of the formulaHO--R¹ --OH, where R¹ is as previously defined. Said second salt may bein the same vessel as the spirobiindane bisphenol salt or may be addedconcurrently with the dicarboxylic acid chloride, with the former methodfrequently affording somewhat higher yields of macrocyclic copolyesters.

Suitable tertiary amines include those previously described withreference to polycarbonates. In general, the quaternary ammonium saltsare somewhat preferred over the tertiary amines. Illustrative quaternaryammonium salts are the tetraalkylammonium halides containing a total ofabout 15-30 carbon atoms, examples of which are tetra-n-butylammoniumbromide and methyltrioctylammonium chloride.

The catalyst is preferably in admixture with said spirobiindanebisphenol salt. Reaction temperatures in the range of about 25°-100° C.and especially about 30°-50° C. are typical.

Anhydrous methods for preparing the macrocyclic polyester oligomers mayalso be employed. They typically utilize the same organic liquids asdiluents and a trialkylammonium salt of the bisphenol.

In a preferred embodiment of the invention, the macrocyclic oligomersare polyamides, polyimides (including polyamideimides), polyetherketonesor polyethersulfones. These compositions will now be described.

Polyamides

In the macrocyclic polyamide oligomers corresponding to formula VI, theR⁵ values may be considered as derived from dicarboxylic acids of theformula R⁵ (COOH)₂, and may be substituted or unsubstituted alkylene orarylene (other than o-arylene) radicals. The alkylene radicals generallycontain about 2-8 carbon atoms, about 2-4 thereof usually being in astraight chain. They are illustrated by ethylene, trimethylene andtetramethylene, as well as branched isomers thereof. The aryleneradicals, which are preferred, generally contain about 6-25 carbon atomsand are illustrated by m-phenylene, p-phenylene, the correspondingtolylene radicals, 4,4'-biphenylene, 1,4-naphthylene, 1,8-naphthyleneand divalent phenylindane radicals of the formula ##STR17## wherein R²and n are as previously defined. Spirobiindane radicals are alsoincluded. Any substituent which does not undergo interfering reactionsin the context of this invention may be present thereon. Illustrativesubstituents are halo, nitro, hydroxy and alkoxy. The arylenehydrocarbon radicals, especially m-phenylene, are most preferred.

The R⁴ radicals are most often unsubstituted m- or p-phenylene. Thevalue of p may be 0 or 1; that is, the --O--R⁴ --moiety may be presentor absent.

Polyamide oligomers corresponding to formula VII are also within thescope of the invention. In that formula, A⁴ may be, for example,m-phenylene, p-phenylene or a disiloxane radical of formula VIII,wherein the disiloxane moiety is flanked by two alkylene, cycloalkyleneor arylene radicals. Any R³ alkylene radicals for this purpose generallycontain 2-4 carbon atoms. The substituents on silicon may be alkyl,phenyl or substituted phenyl and are most often methyl.

The macrocyclic polyamide oligomer compositions of this inventioninclude oligomers having degrees of polymerization from 1 to about 15.For the most part, said compositions are mixtures of oligomers havingvarying degrees of polymerization. However, it is frequently possible toisolate individual oligomers, particularly the cyclic "monomer", byconventional means such as preparative scale high pressure liquidchromatography. Higher oligomer species are hereinafter sometimesidentified as "dimer", etc.

Said oligomer compositions may be prepared from the correspondingdiamines and dicarboxylic acid chlorides, as described hereinafter. Thediamines in which R4 is m- or p-phenylene and p is 1, and correspondingnitro compounds, are novel compounds; they are disclosed and claimed inthe aforementioned application Ser. No. 20,264.

The nitro compounds (hereinafter sometimes "bisnitrophenoxy ethers") maybe prepared by the reaction of halonitrobenzenes or dinitrobenzenes withspirobiindane bisphenol salts under alkaline conditions in a dipolaraprotic solvent. The molar ratio of nitro compound to spirobiindanebisphenol salt is generally about 2.0-2.5:1. The correspondingbis-aminophenoxy ethers may be prepared by reduction of saidbis-nitrophenoxy ethers by conventional means such as catalytichydrogenation.

The preparation of the bis-nitrophenoxy and bis-aminophenoxy ethers isillustrated by the following examples.

EXAMPLE 1

A reaction vessel fitted with a mechanical stirrer, reflux condenser andnitrogen purge means was charged with 45.9 grams (149 mmol.) of SBI,49.31 grams (303 mmol.) of p-chloronitrobenzene, 61.68 grams (447 mmol.)of potassium carbonate and 700 ml. of dry dimethylformamide. The mixturewas purged with nitrogen and heated at 150° C. with stirring for 14hours. It was then poured into 1.5 liters of ice water with rapidstirring, and the precipitated 6,6'-bis(4-nitrophenoxy)-3,3,3',3'-tetramethyl-1,1'-spiro(bis)indane was recrystallized from methylethyl ketone. The yield was 73.7 grams (90% of theoretical) of acrystalline product, m.p. 200.5°-201.5° C. The structure was confirmedby elemental analysis.

EXAMPLE 2

A mixture of 5.27 grams (9.58 mmol.) of the product of Example 1, 100mg. of platinum oxide and 100 ml. of tetrahydrofuran was pressurizedwith hydrogen at 50 psi. and shaken for 3 hours at room temperature. Themixture was filtered, using a filter aid material, and the filtrationresidue was washed with methylene chloride. The combined filtrates werevacuum stripped to yield 4.6 grams (98% of theoretical) of6,6'-(4-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spiro(bis)indane, whichwas recrystallized from toluene to yield the pure product as finecrystals, m.p. 214°-215° C. The structure was confirmed by elementalanalysis.

EXAMPLE 3

In a reaction vessel similar to that of Example 1, a mixture of 24.51grams (79.6 mmol.) of SBI, 27.40 grams (163.1 mmol.) ofm-dinitrobenzene, 43.93 grams (318.4 mmol.) of potassium carbonate and175 ml. of dimethyl sulfoxide was heated for 30 hours at 140° C., undernitrogen. The mixture was cooled and diluted with 500 ml. of methylenechloride, and was washed with 10% aqueous sodium hydroxide solution,water and aqueous sodium chloride solution. The organic phase wasfiltered and the filtration residue was rinsed with methylene chloride.The combined filtrates were vacuum stripped to yield 42.5 grams of theproduct as a thick oil. A portion of the oil was purified by mediumpressure liquid chromatography of an ethyl acetate-hexane solution oversilica gel. The purified .[.6,6'-(3-nitrqphenoxy)-3,3,3'.]..Iadd.6,6,'-(3-nitrophenoxy)- 3,3,3'.Iaddend.,3'-tetramethyl-1,1'-spiro(bis)indane was obtained in 66% yield, m.p.174°-175° C. The structure was confirmed by elemental analysis.

EXAMPLE 4

Following the procedure of Example 2, 2.5 grams (4.5 mmol.) of theproduct of Example 3 was hydrogenated over a platinum oxide catalyst.Upon solvent removal and recrystallization from a toluene-cyclohexanemixture, there was obtained 1.8 grams (80% of theoretical) ofanalytically pure6,6'-(3-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spiro(bis)indane, m.p.190°-197° C. with decomposition. The structure was confirmed byelemental analysis.

The macrocyclic polyamide oligomer compositions may be prepared bygradually adding the dicarboxylic acid chloride to a solution in asubstantially inert organic liquid of the diamine, at a temperatureeffective to achieve reaction, said acid chloride and diamine beingemployed in a molar ratio in the range of about 0.8-1.25:1.

Among the suitable intermediates for the polyamide oligomers are the6,6'-diamino- and6,6'-dicarboxy-3,3,3',3'-tetramethyl-bis-1,1'-spiroindanes. Saidcompounds are known in the art and may be prepared, for example, byoxidation of the corresponding 6,6'-dimethyl compounds to dicarboxylicacids followed, for diamine preparation, by treatment with sodium azideand sulfuric acid (i.e., the Schmidt reaction), as described in Curtiset al., J. Chem. Soc., 1962, 418-421.

Any organic liquid which is substantially inert to the diamines and acidchlorides employed may be used in the preparation of the oligomercompositions. In the case of aromatic diamines, suitable liquids includehalogenated alkanes such as methylene chloride and chloroform; aproticpolar solvents such as dimethylformamide, dimethylacetamide and dimethylsulfoxide; aromatic hydrocarbons and chlorinated aromatic hydrocarbonssuch as toluene, xylene and chlorobenzene; and ethers such astetrahydrofuran and ethylene glycol dimethyl ether. In most instances,relatively volatile solvents such as methylene chloride, chloroform andtetrahydrofuran are preferred by reason of the ease of removal thereofby evaporation following completion of the reaction.

In this process of preparation, the acid chloride is gradually added toa solution of the diamine in the organic liquid. It is also most oftenadded in the form of a solution in said liquid. The reagents areemployed in molar ratios in the range of about 0.8-1.25:1 and preferablyabout 0.95-1.05:1.

In one embodiment of the invention, the diamine is initially present inthe reaction vessel. Its concentration should then be up to about 0.03 Mto optimize the yield of cyclics. A second embodiment is to introduceboth reagents simultaneously to said organic liquid, whereupon thediamine is ordinarily also added as a solution.

It is sometimes advantageous to employ a hydrogen chloride acceptor inthe reaction. Suitable hydrogen chloride acceptors are moderately strongbases such as alkali metal carbonates and tertiary amines, preferablysodium carbonate, triethylamine and pyridine. Said acceptor is generallypresent with the diamine, being either in the reaction vessel originallyor introduced simultaneously with the acid chloride. The proportionthereof is preferably at least stoichiometric, most often about 1-3equivalents per calculated equivalent of hydrogen chloride evolved.

Any reaction temperature effective to achieve reaction of the diaminewith the dicarboxylic acid chloride may be employed. Elevatedtemperatures, such as in the range of about 35°-100° C., are usuallysatisfactory, with about 40°-80° C. being preferred.

The above-described macrocyclic polyamide oligomer compositions may alsocontain linear oligomers and high polymer (i.e., linear polyamideshaving a degree of polymerization greater than about 20). Any highpolymer can typically be removed by conventional means such as flashchromatography on silica gel. When employing isophthaloyl dichloride andthe bis-aminophenoxy ethers of this invention, cyclics yields of 90% orgreater are typical.

Polyimides and Polyamideimides

In the polyimides corresponding to formula IX, the Z² value may be anyof the specified linking groups, including those containing a Q valuewhich may be, for example, m- or p-phenylene, a radical derived frombisphenol A or a spirobiindane radical. Polyimides in which Z² or Z³contain amide moieties are, of course, polyamideimides. By reason oftheir facile polymerization, the preferred macrocyclic polyimides arethe polyamideimides, those of formula IX in which Z² is sulfur or adisiloxane moiety, and those of formula X in which Z³ has formula VIII.

The macrocyclic polyimide oligomers may be prepared by reacting anappropriate diamine with an appropriate tetracarboxylic acid orfunctional derivative thereof. Suitable functional derivatives includedianhydrides and bisimides containing electron-deficient N-substituents;the latter are disclosed in U.S. Pat. No. 4,578,470, the disclosure ofwhich is incorporated by reference herein. The dianhydrides arepreferred. Frequent reference to said dianhydrides will be madehereinafter, but it should be understood that the free acids and otherappropriate functional derivatives may be substituted therefor.

The spirobiindane diamines and tetracarboxylic acids and theirderivatives are particularly susceptible to formation of cyclic productsupon reaction with dianhydrides. Therefore, it is not generallynecessary to employ high dilution or other unusual reaction conditionsfor the preparation of the compositions of this invention. For the mostpart, approximately equimolar proportions of diamine and dianhydride areheated at a temperature in the range of about 120°-250° C., with waterof reaction being removed by distillation. It is frequently preferred toemploy a relatively high boiling organic solvent, typically achlorinated aromatic hydrocarbon such as o-dichlorobenzene or a dipolaraprotic solvent such as dimethyl sulfoxide or dimethylacetamide. Thepresence of a metal carboxylate or oxygenated phosphorus compound as acatalyst, in accordance with U.S. Pat. Nos. 4,293,683 and 4,324,882, isalso often beneficial. The disclosures of these patents are alsoincorporated by reference herein.

Tetracarboxylic acids of the formula R1 ? ##STR18## and their functionalderivatives are novel compounds and are disclosed and claimed incopending, commonly owned application Ser. No.146,153 filed Jan. 20,1988. The bisimides may be prepared by the reaction of the correspondingspirobiindane bisphenols with nitro-N-alkylphthalimides and converted todianhydrides by methods similar to those employed to prepare thecorresponding bisphenol A reaction products. The following example isillustrative.

EXMAPLE 5

SBI, 15.4 grams (50 mmol.), was added portionwise to a slurry of 262grams (102 mmol.) of sodium hydride in 100 ml. of dry dimethylformamide.The mixture was heated for one hour at 75° C in a nitrogen atmosphere,after which 20.6 grams (100 mmol.) of 4-nitro-N -methylphthalimide wasadded. The resulting mixture was heated for 11/2 hours at 110° C.,cooled and poured into 3 volumes of cold water. The solid whichprecipitated was filtered and suspended in a mixture of toluene and 2%aqueous sodium hydroxide solution and the mixture was cooled andfiltered; the organic phase of the filtrate was dried and vacuumstripped. The combined solids were the desired6,6'-bis(3,4-dicarboxyphenoxy) -3,3,3',3'-tetramethylspiro(bis)indanebis-N-methylimide (27.07 grams, 86.5% of theoretical). Its melting pointafter recrystallization from toluene was 217.5°-218° C. The structurewas confirmed by proton nuclear magnetic resonance and field desorptionmass spectrometry.

A solution of 14 grams (22.36 mmol.) of the bisimide in 16.7 grams of a45% aqueous potassium hydroxide solution and 20 ml. of water was heatedunder reflux, with water and methylamine being removed by distillationand water being replenished. Heating was continued for 4 days, until thedistillate was neutral to pH paper. The solution was cooled and addedslowly to cold concentrated hydrochloric acid, and the tetracarboxylicacid which precipitated was collected by filtration, dried and dissolvedin a mixture of 25 ml. of chlorobenzene and 5 ml. of acetic anhydride.Upon heating under reflux for 21/2 hours and cooling, the desireddianhydride (10.3 grams, 77% of theoretical) precipitated and wasfiltered and dried; it melted at 233°-234° C. The structure wasconfirmed spectroscopically as for the bisimide.

Polyamideimides may be prepared by methods similar to those employed forthe preparation of polyimides, employing a tricarboxylic acid orfunctional derivative thereof instead of the tetracarboxylic acid or adiamine containing an amide moiety. The tricarboxylic acid, when used(and the corresponding R⁹ radical), may be aliphatic, alicyclic oraromatic and is preferably aromatic. An especially preferred acidderivative is trimellitic anhydride acid chloride (TAAC).

Polyetherketones and Polyethersulfones

In the compounds corresponding to formula XI, the A⁵ radical may be anyaromatic radical which contains at least one carbonyl or sulfone group.Illustrative radicals of this kind are bis(4-phenylene)sulfone, thecorresponding radical derived from benzophenone and the 1,8-divalent9,10-anthraquinone radical.

The macrocyclic polyetherketone and polyethersulfone oligomers may beprepared by the reaction of a spirobiindane bisphenol with acorresponding dihalo (preferably difluoro or dichloro) ketone or sulfonein the presence of a basic reagent such as potassium carbonate, whichpromotes the requisite nucleophilic aromatic substitution reaction. Arelatively high boiling dipolar aprotic solvent such as dimethylsulfoxide is preferred, and suitable reaction temperatures are generallyin the range of about 120°-180° C. Molar ratios of spirobiindanebisphenol to dihalo compound are generally 1:1 or very close thereto,and the amount of base is most often about 2.0-2.5 moles per mole ofspirobiindane bisphenol.

The preparation of the macrocyclic oligomer compositions of thisinvention is illustrated by the following examples.

EXAMPLE 6

A mixture of 31.7 grams (100 mmol.) of spirobiindane bisphenol, 30 grams(200 mmol.) of N,N-diethylaniline and 500 ml. of methylene chloride wascooled to -10° C. with stirring. Phosgene was bubbled through thesolution at 3 grams per minute for 10 minutes (total 300 mmol.).Stirring was continued as the mixture was allowed to warm slowly to roomtemperature over 2 hours. It was warmed in a water bath and sparged withnitrogen to evaporate about half the methylene chloride, diluted with anequal volume of hexane and washed three times with dilute aqueoushydrochloric acid and once with water. The organic layer was filteredand vacuum stripped, and the resulting oil was dissolved in petroleumether and filtered. Upon stripping of the petroleum ether, the desiredspirobiindane bisphenol bischloroformate was obtained; it comprisedabout 90% monomer bischloroformate.

A mixture of 80 ml. of methylene chloride, 10 ml. of water, 0.5 ml. of50% aqueous sodium hydroxide and 0.51 ml. of triethylamine was heated toreflux with stirring. There was added over 30 minutes, with continuedstirring, 50 ml. of a 1 M solution in methylene chloride of equimolarproportions of bisphenol A bischloroformate and spirobiindane bisphenolbischloroformate. At the same time, 5 ml. of 50% aqueous sodiumhydroxide and 0.525 ml. of triethylamine were added in 5 increments at5-minute intervals. When the addition was complete, the organic andaqueous layers were separated and the aqueous layer was washed withmethylene chloride. The combined organic phases were washed three timeswith dilute aqueous hydrochloric acid and once with water, filtered andvacuum stripped to yield the desired mixed macrocyclic polycarbonateoligomers.

EXAMPLE 7-11

Following the procedure of Example 6, macrocyclic bisphenol A-SBIcopolycarbonate oligomer compositions having the following proportionswere prepared:

    ______________________________________                                                                Bisphenol A,                                          Example      SBI, mole %                                                                              mole %                                                ______________________________________                                        7            75         25                                                    8            65         35                                                    9            35         65                                                    10           25         75                                                    11           10         90                                                    ______________________________________                                    

In Examples 7-10, reagent A was a mixture of the bischloroformates ofSBI and bisphenol A; in Example 11, it was a mixture of bisphenol Abischloroformate and free SBI.

EXAMPLE 12

Phosgene was passed at 1 gram per minute into a mixture of 15.85 grams(50 mmol.) of spirobiindane bisphenol, 10 ml. of 2.5 M aqueous sodiumhydroxide and 100 ml. of methylene chloride until a clear solution wasobtained, at which point the pH dropped below 7. Phosgene passage wascontinued for a total of 12 minutes at a pH in the range of 4-6. Thecrude spirobiindane bisphenol bischloroformate composition was isolatedas in Example 6; it was found to contain about 45% monomerbischloroformate, about 28% dimer bischloroformate and about 15% trimerbischloroformate.

Following the procedure of Example 6, a macrocyclic spirobiindanebisphenol homopolycarbonate mixture was prepared from the crudebischloroformate.

EXAMPLE 13

A three-necked, 50 ml. Morton flask equipped with a reflux condenser,mechanical stirrer and septum cap was charged with 11 ml. of methylenechloride, 2 ml. of water, 48 microliters of triethylamine and 0.15 ml.of 4 M aqueous sodium hydroxide solution. The mixture was heated to 45°C., with mechanical stirring at a rate just sufficient to disperse thewater in the methylene chloride. There were then added simultaneously,via four syringes, a solution of 1.04 grams of SBI bischloroformate in 5ml. of methylene chloride, a solution of 110 mg. of2-(4-hydroxyphenyl)-2-4-(3,5-dimethyl-4-hydroxyphenoxy)phenyl]propane(prepared, for example, as described in Example 9 of U.S. Pat. No.3,496,236) in 2 ml. of methylene chloride, a solution of 25 microlitersof triethylamine in 75 microliters of methylene chloride, and 1.35 ml.of the aqueous sodium hydroxide solution. One-tenth of the contents ofeach syringe was charged to the reaction vessel every 3 minutes, for atotal addition time of 30 minutes. There were thus provided, per mole ofSBI bischloroformate: 130 mmol. of bisphenol, 440 mmol. of triethylamineand 5 moles of sodium hydroxide.

The mixture was stirred for an additional 3 minutes and diluted with 100ml. of methylene chloride. The organic phase was washed twice withaqueous hydrochloric acid solution and once with aqueous sodium chloridesolution, filtered through phase separation paper and vacuum stripped.The product which separated as a white flaky solid was shown by highpressure liquid chromatography to comprise 25% high polymer, about 36%cyclic SBI homopolycarbonate and about 36% mixed macrocyclicpolycarbonate oligomers. Upon analysis by field desorption massspectroscopy, the following oligomers were detected:

    ______________________________________                                        Formula IV     Formula XIV                                                    units          units                                                          ______________________________________                                        1              1                                                              2              1                                                              3              1                                                              4              1                                                              2              3                                                              3              2                                                              ______________________________________                                    

No linear oligomers were found.

EXAMPLE 14

A solution of 18.22 grams of poly(2,6-dimethyl -1,4-phenylene ether)having a number average molecular weight of 20,000 as determined by gelpermeation chromatography, 6.92 grams of bisphenol A and 200 ml. oftoluene was heated to 120° C., with stirring, as 420 milligrams of3,3'5,5'-tetramethyl-4,4'-diphenylquinone was added in three equalportions at 1-hour intervals. The mixture was heated for an additional 4hours and vacuum stripped. The residue was dissolved in 200 ml. ofmethylene chloride and refrigerated at 3° C., whereupon unreactedpolyphenylene ether precipitated as the methylene chloride complex.

The filtrate was vacuum stripped to afford 23.3 grams of a yellow solidshown by field desorption mass spectroscopy to comprise oligomers offormula XV wherein each Y³ is hydrogen. A major proportion of thecompounds detected had a value for x of less then 16, with said value ina large proportion being less than 5.

A reaction vessel identical to that of Example 13 was charged with 10ml. of methylene chloride, 1.5 ml. of water, 0.16 ml. of aqueous sodiumhydroxide solution and 51 microliters of triethylamine. Following theprocedure of Example 1, there were then added a solution of 1.09 gramsof SBI bischloroformate in 4 ml. of methylene chloride, a solution of290 mg. of the above-prepared oligomer composition in 2 ml. of methylenechloride, a solution of 26 microliters of triethylamine in 74microliters of methylene chloride and 1.4 ml. of aqueous sodiumhydroxide solution. There were thus provided, per mole of SBIbischloroformate: 130 mmol. of bisphenol, 440 mmol. of triethylamine and5 moles of sodium hydroxide.

Upon workup and isolation as described in Example 13, there was obtained1.2 grams of a flaky solid which was shown by high pressure liquidchromatography to comprise 40% high polymer, about 30% macrocyclic SBIhomopolycarbonate oligomers and about 30% mixed macrocyclic oligomers.The latter were shown by field desorption mass spectrometry to includemolecular species containing one unit of formula XIV and the followingother structural details:

    ______________________________________                                               Formula IV                                                                    units    x                                                             ______________________________________                                               1        2                                                                    2        1                                                                    2        3                                                             ______________________________________                                    

No linear oligomers were detected.

EXAMPLE 15

A mixture of 31.7 grams (100 mmol.) of SBI hemihydrate, 50 ml. of 5 Maqueous sodium hydroxide solution (250 mmol.) , 645 mg. (2 mmol.)etra-n-butylammonium bromide and 200 ml. of methylene chloride washeated under reflux and 100 ml. of a 1 M solution of isophthaloylchloride in methylene chloride was added over 30 minutes. After theaddition was complete, refluxing was continued for 5 minutes. Theaqueous and organic phases were separated and the aqueous phase wasextracted with methylene chloride; the extracts were combined with theorganic phase and washed with aqueous hydrochloric acid solution,aqueous sodium chloride solution and water. Upon evaporation of themethylene chloride, there was obtained a product which was found by highpressure liquid chromatographic analysis to contain 85% macrocyclicpolyarylate oligomers and 15% linear polymer. The identities of theoligomers were confirmed by infrared and nuclear magnetic resonancespectroscopy.

EXAMPLE 16

The procedure of Example 15 was repeated, substituting terephthaloylchloride on an equimolar basis for the isophthaloyl chloride. A productwas obtained which comprised 50% macrocyclic polyarylate oligomers and50% linear polyarylate.

EXAMPLE 17

To a mixture of 310 mg. (2.5 mmol.) of 4-dimethylaminopyridine in 50 ml.of methylene chloride was added under reflux over 30 minutes, withstirring, 25 ml. of a methylene chloride solution 1 M in SBI and 2.2 Min triethylamine, and 25 ml. of a 1 M solution of isophthaloyl chloridein methylene chloride. There were then added an excess of 1 M aqueoushydrochloric acid solution and additional methylene chloride. Theorganic phase was washed with water, concentrated, dissolved inchloroform and analyzed by gel permeation chromatography; it was foundto contain 70% of the theoretical amount of macrocyclic SBI polyarylateoligomers.

EXAMPLE 18

A solution of 20.3 grams (10 mmol.) of isophthaloyl chloride in 10 ml.of methylene chloride was added over 30 minutes, with stirring, to amixture of 2.01 grams (8.8 mmol.) of bisphenol A, 680 mg. (2.2 mmol.) ofSBI, 880 mg. (22 mmol.) of sodium hydroxide, 32 mg. of tetra-n-butylammonium bromide, 20 ml. of methylene chloride and 5 ml. of water.Upon workup as described in Example 15, there was obtained a productwhich was found by gel permeation chromatography to contain about 55%macrocyclic copolyarylate oligomers.

EXAMPLE 19

To a mixture of 680 mg. (2.2 mmol.) of SBI, 180 mg. (4.4 mmol.) ofsodium hydroxide, 32 mg. of tetra-n-butylammonium bromide, 10 ml. ofmethylene chloride and 2 ml. of water were added over 30 minutes, withstirring, 17.6 ml. (8.8 mmol.) of a 0.5 M aqueous solution of bisphenolA disodium salt and 10 ml. (10 mmol.) of a 1 M solution of isophthaloylchloride in methylene chloride. Upon workup as described in Example 15,there was obtained a product which was shown by gel permeationchromatography to contain about 40% macrocyclic copolyarylate oligomers.

EXAMPLE 20

A reaction vessel fitted with a septum cap, a reflux condenser andnitrogen purge means was charged with 5 ml. of chloroform which wasbrought to reflux in a nitrogen atmosphere. There were simultaneouslyadded over 1/2 hour, via two syringes, a solution of 505.4 mg. (1.03mmol.) of the diamine of Example 2 and 213 mg. (2.11 mmol.) oftriethylamine in 5 ml. of dry tetrahydrofuran, and a solution of 209 mg.(1.03 mmol.) of isophthaloyl chloride in 5 ml. of dry chloroform.Refluxing was continued for 5 minutes, after which the mixture wasdiluted with 50 ml. of chloroform, washed with dilute aqueoushydrochloric acid solution and with sodium chloride solution, filteredthrough phase separation paper and vacuum stripped, yielding 520 mg.(80% of theoretical) of the desired cyclic polyamide oligomer mixture,m.p. 245°-285° C. It was shown by high pressure liquid chromatography tocontain macrocyclic oligomers with degrees of polymerization up to about15, with monomer to hexamer species being present in the approximateratios 78:28:8:4:2:1. The presence of the monomer and dimer wasconfirmed by field desorption mass spectrometry.

The cyclic monomer species was isolated by preparative scale highpressure liquid chromatography. Its identity was also confirmed by fielddesorption mass spectrometry.

EXAMPLE 21

A reaction system similar to that of Example 20 was charged with 62 ml.of chloroform which was brought to reflux in a nitrogen atmosphere.There were simultaneously added over 40 minutes a solution of 1 gram(2.04 mmol.) of the diamine of Example 4 and 490 mg. (4.85 mmol.) oftriethylamine in 10 ml. of dry tetrahydrofuran, and a solution of 500mg. (3.46 mmol.) of isophthaloyl chloride in 10 ml. of dry chloroform.Refluxing was continued for 15 minutes, after which the mixture wasdiluted with methylene chloride, washed with dilute aqueous hydrochloricacid solution and vacuum stripped, yielding 1.33 grams of the desiredmacrocyclic polyamide oligomer mixture. It was shown by high pressureliquid chromatography to contain monomer to heptamer species in theapproximate ratios 18.9:5.6:1.2:1.6:1.3:0.9:1.

EXAMPLE 22

A solution of 1 gram (2 mmol.) of the diamine of Example 2 and 410 mg.(4 mmol.) of triethylamine in 36 ml. of dry tetrahydrofuran was heatedto reflux and a solution of 410 mg. (2 mmol.) of isophthaloyl chloridein 5 ml. of chloroform was added over 1/2 hour. Upon workup as inExample 20, there was obtained a product shown by high pressure liquidchromatography to contain over 90% macrocyclic polyamide oligomers, withmonomer to octamer species being present in the approximate ratios18.4:7.9:4.5:2.9:2.0:1.6:1.2:1.

EXAMPLE 23

Following the procedure of Example 22, a solution of 2 mmol. ofisophthaloyl chloride in 5 ml. of chloroform was added to a mixture of 2mmol. of the diamine of Example 2, 650 mg. (6 mmol.) of sodium carbonateand 200 ml. of dry chloroform. Upon workup, there was obtained 1.2 gramsof a tan solid containing about 90% macrocyclics, with monomer tohexamer species being present in the approximate ratios11.0:3.6:2.3:1.4:1.2:1.

EXAMPLE 24

Following the procedure of Example 22, a solution of 2 mmol. ofisophthaloyl chloride in 5 ml. of chloroform was added to a solution of2 mmol. of the diamine of Example 2 in 77 ml. of dry chloroform, in theabsence of hydrogen chloride acceptors. There was obtained 900 mg. of ayellow solid containing 90% macrocyclics, with monomer to hexamerspecies being present in the approximate ratios 16.2:3.1:1.7:1.0:1.1:1.

EXAMPLES 25-26

The procedure of Example 22 was repeated substituting4,4'-biphenyldicarboxylic acid chloride and 1,1,3-trimethyl-3-phenylindane-4',6-dicarboxylic acid chloride, respectively,for isophthaloyl chloride on an equimolar basis. The products were shownto contain the following approximate ratios of molecular species:

Example 25--monomer to decamer,

7.4:7.3:4.4:3.1:2.3:2.1:1.6:1.4:1.2:1.

Example 26--monomer to heptamer,

.[.4.45.211.3:6.33.3:1.7:1.]. .Iadd.4.4:5.2:11.3:6.3:3.3:1.7:1.Iaddend..

EXAMPLE 27

To a reaction vessel containing 12 ml. of dry methylene chloride atreflux temperature were added over 1/2 hour under nitrogen, withstirring, a solution of 200 mg. hydroxide (0.65 mmol.) of6,6'-diamino-3,3,3', 3'-tetramethyl-1,1'-spiroindane and 132 mg. (1.3mmol.) of triethylamine in 4 ml. of methylene chloride, and a solutionof 133 mg. (0.65 mmol.) of isophthaloyl chloride in 4 ml. of methylenechloride. The mixture was cooled to room temperature, diluted with 50ml. of methylene chloride, washed twice with dilute aqueous hydrochloricacid solution and once with aqueous sodium chloride solution, dried overmagnesium sulfate and vacuum stripped. There was obtained 270 mg. of awhite solid which was shown by high pressure liquid chromatography andfield desorption mass spectroscopy to contain approximately 50%macrocyclic polyamide oligomers, with the balance being linear oligomersand high polymer.

EXAMPLE 28

A reaction vessel fitted with a septum cap, a magnetic stirrer, a refluxcondenser and nitrogen purge means was charged with a solution of 840mg. (1.71 mmol.) of the diamine of Example 2 and 270 mg. (3.42 mmol.) ofpyridine in 20 ml. of chloroform which was brought to reflux in anitrogen atmosphere. There was added over one hour, via a syringe, asolution of 1 gram (1.71 mmol.) of the diacid chloride of6,6'-dicarboxy-3,3,3',3'-tetramethyl-1,1'-spiro(bis)indane in 14 ml. ofdry chloroform. Refluxing was continued for 15 minutes, after which themixture was diluted with 100 ml. of chloroform, washed with diluteaqueous hydrochloric acid solution and with sodium chloride solution,dried over magnesium sulfate, filtered and vacuum stripped, yielding 850mg. of the desired macrocyclic polyamide oligomer mixture.

EXAMPLES 29-31

Following the procedure of Example 21, various diamines were reactedwith equimolar proportions of the diacid chloride of6,6'-dicarboxy-3,3,3',3'-tetramethyl- 1,1'-spiro(bis)indane. Afterwashing, the organic phases were dried over magnesium sulfate, filteredand vacuum stripped. The products were shown by high pressure liquidchromatography and field desorption mass spectrometry to comprisemacrocyclic amide oligomers having degrees of polymerization from 1 to3. The diamines employed were:

Example 29--m-phenylenediamine;

Example 30--4-aminophenyl ether;

Example 31--2.2-bis(4-aminophenyl)propane.

EXAMPLE 32

To a solution of 1.081 grams (10 mmol.) of mphenylenediamine and 18 mg.of sodium phenylphosphonate in 120 ml. of o-dichlorobenzene was addedslowly at 130° C., with stirring, a solution of 6 grams (10 mmol.) ofthe dianhydride of Example 5 in 60 ml. of hot o-dichlorobenzene. Heatingat 130° C. was continued for 11/2 hours, after which the temperature wasraised to 225° C. and water and solvent were removed by distillation toa total of 90 ml. The solution was heated under reflux for 3 hours,cooled and poured into 600 ml. of methanol. The solids whichprecipitated were extracted in a Soxhlet extractor with acetone for 18hours. The residue from the extraction was a linear polyimide having aweight average molecular weight greater than 100,000. Upon evaporationof the acetone from the extracts, there was obtained a white powderwhich was shown by field desorption mass spectrometry to compriseprincipally the macrocyclic polyetherimide dimer. The yield was about75% of theoretical.

EXAMPLES 33-36

The procedure of Example 32 was repeated, substituting the followingdiamines for the m-phenylenediamine on an equimolar basis:

Example 33--p-phenylenediamine;

Example 34--bis(4-aminophenyl)methane;

Example 35--4-aminophenyl ether;

Example 36--9,9,bis(4-aminophenyl)fluorene.

The product of Example 33 was insoluble in methanol and comprised amixture of linear polyetherimide and macrocyclic oligomers.

EXAMPLE 37

A dry blend of 652 mg. (2 mmol.) of bis(3,4-dicarboxyphenyl) sulfidedianhydride, 1043 mg. (2 mmol.) of BPADA, 1960 mg. (4 mmol.) of thediamine of Example 2 and 40 mg. of sodium phenylphosphonate was addedover 45 minutes, with stirring, to 120 ml. of o-dichlorobenzenemaintained at 140° C. The resulting solution was distilled slowly withremoval of 60 ml. of distillate, including water of reaction. It wasthen heated under reflux for 3 hours, after which the solution wasconcentrated to about 20-25 ml. by distillation, cooled, poured into anexcess of methanol and agitated in a blender. Upon filtration and dryingof the residue in a vacuum oven, there was obtained 2.76 grams (79% oftheoretical) of a solid product which was shown by liquidchromatographic analysis to be a mixture of macrocyclic polyimides andlinear polymer comprising about 80% cyclics.

One gram of the crude product was extracted for 24 hours with acetone ina Soxhlet extractor. Upon precipitation from the acetone extract, therewas obtained 300 mg. of a mixture of macrocyclic polyimidessubstantially free of linear polymer. It was shown by field desorptionmass spectroscopy to contain the macrocyclic "monomer" containing oneunit of formula IX, the corresponding "monomer" of the diamine andBPADA, the macrocyclic "dimer" of the diamine andbis(3,4-dicarboxyphenyl) sulfide and the mixed "dimer". The residue fromthe extraction, comprising linear polyimide, had a glass transitiontemperature of 233° C.

EXAMPLE 38

A mixture of 1.956 grams (6 mmol.) of bis(2,3-dicarboxyphenyl) sulfide,2.94 grams (6 mmol.) of the diamine of Example 2 and 60 mg. of sodiumphenylphosphonate was added to o-dichlorobenzene and treated as inExample 37. The solid product (4.62 grams, or 98.7% of theoretical) wasshown by liquid chromatographic analysis to comprise 80% cyclics. Uponextraction by acetone, 950 mg. of cyclics substantially free of linearpolymer was obtained; field desorption mass spectroscopy showed thepresence of the macrocyclic monomer and dimer. The residue from theextraction, comprising linear polyimides, had a glass transitiontemperature of 250.2° C.

EXAMPLE 39

A dry blend of 100 mg. (0.33 mmol.) of6,6'-di-amino-3,3,3',3'-tetramethyl-1,1'-spiro(bis) indane and 107 mg.(0.33 mmol.) of bis(2,3-dicarboxyphenyl) sulfide dianhydride is addedover 30 minutes, with stirring, to a mixture of 20 ml. ofo-dichlorobenzene and 1 mg. of sodium phenylphosphonate maintained at100° C. The mixture is maintained at that temperature for 2 hours andthen distilled until 5-7 ml. of distillate, including water of reaction,has been collected. It is then heated under reflux for 5 hours. Uponworkup and extraction as in Example 37, the desired macrocyclic productis obtained.

EXAMPLE 40

To a solution of 1.03 grams (4.54 mmol.) of 3,3'-diaminobenzanilide and15 mg. of sodium pyrophosphate in 280 ml. of o-dichlorobenzene was addedunder reflux over 1/2 hour, with stirring, a solution of 2.72 grams(4.54 mmol.) of the dianhydride of Example 5 in 30 ml. of warmo-dichlorobenzene. Refluxing was continued for 2 hours, after which thewater and solvent were removed by distillation to a total of 180 ml. Thesolution was cooled and poured into 500 ml. of rapidly stirred methanol.The solids which precipitated were extracted in a Soxhlet extractor withacetone. The residue from the extraction was a linear polyamideimide.Upon evaporation of the acetone from the extracts, there was obtained awhite powder which was shown by field desorption mass spectrometry tocomprise principally the macrocyclic polyamideimide dimer. The yield wasabout 70% of theoretical.

EXAMPLE 41

To a solution of 1 gram (2.04 mmol.) of trimellitic anhydride acidchloride and 15 mg. of sodium pyrophosphate in 2 ml. ofo-dichlorobenzene was added slowly at 100° C., with stirring, a solutionof 430 mg. (2.04 mmol.) of the diamine of Example 2 in 1 ml. ofo-dichlorobenzene. The mixture was heated at 180° C. for 1 hour and 5ml. of o-dichlorobenzene was added. Water and solvent were removed bydistillation to a total of 50 ml., after which o-dichlorobenzeneaddition and distillation were repeated. The solution was cooled andpoured into 50 ml. of rapidly stirred methanol. The solids whichprecipitated were filtered to yield 1.2 grams (91% of theoretical) of amaterial which was shown by high pressure liquid chromatography andfield desorption mass spectrometry to comprise principally themacrocyclic polyamideimide dimer.

EXAMPLE 42

A solution of 1.274 grams (5 mmol.) of1,9-di-amino-4,4,6,6-tetramethyl-4,6-disila-5-oxanonane in 50 ml. ofo-dichlorobenzene was added over 1 hour to a solution of 3 grams (5mmol.) of the dianhydride of Example 5 and 2 mg. of sodiumphenylphosphonate in 250 ml. of o-dichlorobenzene, at 140° C. When theaddition was completed, the temperature was raised to 225° C. ando-dichlorobenzene and water were removed by distillation until thedistillate was no longer cloudy; a total of about 100 ml. ofo-dichlorobenzene was thus removed. The residual solution was heatedunder reflux for 2 hours and then reduced to about 10% of its originalvolume by distillation. Upon cooling and pouring into 5 volumes ofmethanol, a solid precipitated which was collected by filtration anddried in a vacuum oven at 110° C. It was shown by field desorption massspectrometry to comprise the desired macrocyclic siloxane polyetherimidemonomer and dimer. A further portion of macrocyclic monomer was obtainedby evaporation of the methanol from the filtrate. The total yield ofmacrocyclic oligomers was 3.34 grams, or 82% of theoretical.

EXAMPLE 43

The procedure of Example 42 was repeated, replacing the diamine on anequimolar basis with bis(3-aminophenyl)tetramethyldisiloxane. There wasobtained 3.87 grams (85% of theoretical) of a white solid comprising amixture of linear siloxane polyetherimide and macrocyclic oligomers.

EXAMPLE 44

A solution of 11 grams (22 mmol.) of the diamine of Example 2 and 10 mg.of sodium pyrophosphate in 1000 ml. of o-dichlorobenzene was heatedunder reflux, with stirring, and a solution of 9.42 grams (22 mmol.) of1,3-bis(3,4-dicarboxyphenyl)tetramethyldisiloxane dianhydride in 120 ml.of o-dichlorobenzene was added over 1/2 hour. The mixture was heatedunder reflux for 2 hours, after which about 200 ml. of solvent wasremoved by distillation and refluxing was continued for another 3 hours.The solution was concentrated by distillation to about 200 ml., cooledand added to 1 liter of hexane, with stirring. A solid productprecipitated and was collected by filtration and air-dried. The yieldwas 18.5 grams, or 94% of theoretical. It was shown by high pressureliquid chromatography and field desorption mass spectrometry to include90% macrocyclic siloxane polyetherimide oligomers having degrees ofpolymerization from 1 to 5, and 10% linear siloxane polyetherimide. Uponrecrystallization from o-dichlorobenzene, there was obtainedsubstantially pure macrocyclic monomer melting at 295°-299° C.

EXAMPLE 45

To a mixture of 100 ml. of dimethyl sulfoxide, 50 ml. of toluene and2.073 grams (20.9 mmol.) of potassium carbonate were added undernitrogen, with stirring, 2.543 grams (10 mmol.) of bis(4-fluorophenyl)sulfone and 3.084 grams (10 mmol.) of SBI. The mixture was heated at140°-150° C. for 4 hours, cooled and poured into 400 ml. of methanol,whereupon the desired macrocyclic polyethersulfone oligomersprecipitated as a white solid which was filtered and dried for 3 hoursin a vacuum oven at 100° C. The yield was 4.73 grams (90% oftheoretical).

EXAMPLES 46-49

The procedure of Example 45 was repeated, substituting other haloarylcompounds for the bis(4-fluorophenyl)sulfone. The compounds employed andyields of macrocyclic oligomers obtained were as follows:

Example 46--4,4'-difluorobenzophenone, 47%;

Example 47--4-(4-fluorobenzoyl)phenyl ether, 40%;

Example 48--4-(4-fluorobenzoyl)phenyl sulfide, 48%;

Example 49--1,8-dichloro-9,10-anthraquinone, 52%.

EXAMPLE 50

A reaction vessel fitted with a thermometer, septum cap and Dean-Starktrap fitted with a condenser was charged with 100 ml. of dimethylsulfoxide, 50 ml. of toluene and 2.073 grams (20.9 mmol.) of finelyground potassium carbonate. A solution of 3.084 grams (10 mmol.) of SBIand 2.543 grams (10 mmol.) of bis(4-fluorophenyl) sulfone in 12 ml. ofdimethyl sulfoxide was added at 140°-150° C., with stirring, over 21/2hours. Heating was continued for 3 hours after which the toluene wasremoved by distillation and the mixture was cooled to room temperatureand poured into 400 ml. of methanol. The product, comprising macrocyclicpolyethersulfone oligomers, was separated by filtration and dried in avacuum oven at 100° C. The yield was 4.073 grams (78% of theoretical).Field desorption mass spectrometric analysis showed the presence of themacrocyclic polyethersulfone dimer and trimer.

EXAMPLES 51-52

The procedure of Example 50 was repeated, substituting bisphenol A and4,4'-dihydroxybiphenyl on an equimolar basis for half the SBI. Theyields of macrocyclic oligomers were 76% and 65%, respectively, oftheoretical.

The macrocyclic oligomers of this invention may be converted tocorresponding linear polymers, which have uses typical of known polymersof these types. The method of conversion to linear polymers will dependon the linking groups present in the macrocyclic oligomers.

Macrocyclic polycarbonate oligomers may be converted to linearpolycarbonates by treatment with a polycarbonate formation catalyst.Suitable catalysts include various bases and Lewis acids. It is knownthat basic catalysts may be used to prepare polycarbonates by theinterfacial method, as well as by transesterification and from cyclicoligomers. Such catalysts may also be used to polymerize the cyclicoligomer mixtures. Examples thereof are lithium phenoxide, lithium2,2,2-trifluoroethoxide, n-butyllithium and tetramethylammoniumhydroxide. Also useful are various weakly basic salts such as sodiumbenzoate and lithium stearate.

Another class of basic catalysts is disclosed in U.S. Pat. No.4,701,519, the disclosure of which is also incorporated by referenceherein. It comprises polymers containing alkali metal phenoxide andespecially lithium phenoxide moieties. They are usually present as endgroups, especially on linear polycarbonates having a number averagemolecular weight in the range of about 8,000-20,000 as determined by gelpermeation chromatography relative to polystyrene. Such catalysts may beproduced by reacting a suitable polymer with an alkali metal base,typically at a temperature in the range of about 200°-300° C.

A particularly useful class of Lewis bases, disclosed in U.S. Pat. No.4,605,731, includes numerous tetraarylborate salts, including lithiumtetraphenylborate, sodium tetraphenylborate, sodiumbis(2,2'-biphenylene)borate, potassium tetraphenylborate,tetramethylammonium tetraphenylborate, tetra-n-butylammoniumtetraphenylborate, tetramethylphosphonium tetraphenylborate,tetra-n-butylphosphonium tetraphenylborate and tetraphenylphosphoniumtetraphenylborate. The preferred catalysts within this class are thetetra-n-alkylammonium and tetra-n-alkylphosphonium tetraphenylborates.Tetramethylammonium tetraphenylborate is particularly preferred becauseof its high activity, relatively low cost and ease of preparation fromtetramethylammonium hydroxide and an alkali metal tetraphenylborate.

Lewis acids useful as polycarbonate formation catalysts includedioctyltin oxide, triethanolaminetitanium isopropoxide,tetra(2-ethylhexyl) titanate and polyvalent metal (especially titaniumand aluminum) chelates such as bisisopropoxytitanium bisacetylacetonate(commercially available under the tradename "Tyzor AA") and thebisisopropoxyaluminum salt of ethyl acetoacetate. Among the preferredcatalysts are lithium stearate and bisisopropoxytitaniumbisacetylacetonate.

The linear polycarbonate formation reaction is typically effected, bymerely contacting the cyclic oligomer mixture, either purified or incrude form, with the catalyst at temperatures up to 350° C., preferablyabout 200°-300° C., until polymerization has proceeded to the extentdesired. Although the use of a solvent is within the scope of theinvention, it is generally not preferred. In general, the amount ofcatalyst used is about 0.001-1.0 mole percent based on carbonatestructural units in the oligomer composition.

Conversion of macrocyclic polyester oligomers to linear polyesters isnormally achieved by contacting the macrocyclic oligomer compositionwith a transesterification catalyst at a temperature in the range ofabout 200°-300° C. Compounds useful as catalysts include those known inthe art to be useful for the preparation of linear polyesters fromdihydroxy compounds and alkyl dicarboxylates. These include basiccompounds such as lithium hydroxide, lithium phenoxide and sodiumphenoxide. Also useful are various Lewis acids, especially tetraalkyltitanates such as tetraethyl, tetrabutyl and tetraoctyl titanate. Theamount of catalyst used is generally in the range of about 0.1-1.5 molepercent based on structural units in the macrocyclic polyarylateoligomers. The polymerization reaction is typically carried out in themelt, although solution polymerization in such high boiling solvents as2,4-dichlorotoluene or 1,2, 4-trichlorobenzene are also contemplated, asis solution polymerization in more volatile solvents under pressure.

Macrocyclic polyamide oligomers, as well as polyamideimides, may beconverted to copolyamides by reaction with at least one lactam of theformula ##STR19## wherein R¹⁰ is a divalent aliphatic hydrocarbon orsubstituted hydrocarbon radical containing a chain of about 2-20 carbonatoms, in the presence of a basic reagent. This method and thecopolyamides thus produced are another aspect of the invention.

Any of a number of known lactams may be used. Preferred are those inwhich R¹⁰ is a straight alkylene chain containing about 4-12 carbonatoms. Illustrative lactams are pivalolactam, δ-valerolactam,ε-caprolactam and laurolactam, in which R¹⁰ is CH₂ C(CH₃) ₂, (CH₂)₄,(CH₂)₅ and (CH₂)₁₁, respectively. ε-Caprolactam is especially preferred.

The basic reagents include inorganic bases such as the alkali andalkaline earth metals and their hydrides, hydroxides, carbonates andalkoxides, and strong organic bases such as tetraalkylammoniumhydroxides, guanidines, and organometallics including Grignard reagentsand organolithium reagents. The alkali metal hydrides, especially sodiumhydride, are preferred.

The reaction between the lactam, basic reagent and macrocyclic polyamideoligomer composition typically takes place at elevated temperatures. Ingeneral, temperatures of about 25°-200° C., preferably about 90°-150°C., are adequate to effect reaction of the lactam with the basic reagentto form an anionic intermediate, which subsequently reacts with theoligomer composition at temperatures in the range of about

200°-300° C. The proportions of lactam and oligomer composition are notcritical but may be varied according to the desired stoichiometry of theproduct.

As previously mentioned, the preferred macrocyclic polyimide oligomersof this invention are polyamideimides and those in which Z² is sulfur ora disiloxane moiety, or in which Z³ has formula VIII (i.e., contains adisiloxane moiety), since these functionalities optimize the ease ofconverting said macrocyclic oligomers to linear polyimides.

For example, the macrocyclic polyimides wherein Z² is sulfur may beconverted to linear polyimides by reaction with at least one basicsulfide of the formula M--S--X², wherein M is an alkali metal (usuallysodium) and X² is M or an aryl radical, preferably phenyl. The basicsulfide is generally employed in the amount of about 2-10 mole percent,preferably about 3-6 mole percent, based on structural units in thecyclic imide composition. The polymerization reaction may be conductedin bulk or in solution, typically in a polar aprotic solvent such asdimethylformamide, dimethylacetamide or dimethyl sulfoxide, and isgenerally conducted at temperatures in the range of about 150°-225° C.The polymerization mechanism involves ring-opening of the cyclic imideat the sulfur atom.

Macrocyclic polyimides containing a disiloxane group can be polymerizedby the action of a strongly acidic catalyst such as methanesulfonic ortrifluoromethanesulfonic acid, a basic catalyst such as an alkali metalphenate, or an alkali metal fluoride. Among the latter, cesium fluorideis frequently preferred because of its high solubility in themacrocyclic disiloxane polyimides. It is also possible to incorporate inthe polymerization mixture a cyclic polysiloxane such ascyclooctamethyltetrasiloxane, to increase the molecular weight of thepolysiloxane blocks in the linear polyimide product.

The proportion of catalyst in the mixture, based on macrocyclicpolyimide and cyclic polysiloxane present, may vary widely and istypically about 0.001-10.0 mole percent. Polymerization temperatures aretypically in the range of about 125°-200° C. It may sometimes beadvantageous to employ a non-polar solvent such as o-dichlorobenzene or1,2,4-trichlorobenzene as a reaction medium.

Macrocyclic polyethersulfones and polyetherketones may be converted tocorresponding linear polymers by heating with a catalytic amount,typically about 0.5-2.0 mole percent, of a base. Suitable bases includealkali metal phenates, particularly di-(alkali metal) salts ofbisphenols. Reaction temperatuers of about 350°-400° C. are typical.

The preparation of linear polymers from the macrocyclic oligomercompositions of this invention is illustrated by the following examples.

EXAMPLES 53-54

Tetra-n-butylammonium tetraphenylborate was added to 1 gram each of themacrocyclic copolymeric and homopolymeric spirobiindane bisphenolpolycarbonate oligomers of Examples 6 and 12, and the mixtures weredissolved in 25 ml. of dry methylene chloride. The solutions wereevaporated to dryness under vacuum and further for 4 hours at 110° C. ina nitrogen atmosphere. The solids were heated under nitrogen for 1 hourat 300° C. The polymeric products thus formed were dissolved inmethylene chloride, reprecipitated by pouring into methanol, filteredand dried. The relevant parameters and properties are given in thefollowing table.

    ______________________________________                                        Example                53      54                                             ______________________________________                                        Cyclic product of Example                                                                             6      12                                             Catalyst, mole %      0.12   0.1                                              Mw                  105,400 26,740                                            Tg, °C.       188.4    202                                             ______________________________________                                    

EXAMPLE 55

There were dissolved in 40 ml. of methylene chloride 8 mg. oftetra-n-butylammonium tetraphenylborate and 1.6 grams of the product ofExample 13. The solution was vacuum stripped and the solids were driedat reduced pressure under nitrogen at 110° C. The dried product washeated for 15 minutes at 285° C. under nitrogen. The resultingcopolycarbonate had a weight average molecular weight of 35,000 and anumber average molecular weight of 13,000, both as determined by gelpermeation chromatography relative to polystyrene.

EXAMPLE 56

The procedure of Example 55 was repeated, substituting 1.5 grams of theproduct of Example 14 for the product of Example 13. The resultingcopolycarbonate had a weight average molecular weight of 46,000 and anumber average molecular weight of about 17,600.

EXAMPLE 57

To a solution of 0.5 gram of macrocyclic SBI isophthalate oligomer in 15ml. of methylene chloride was added 1.5 mg. of tetrabutyl titanate. Thesolution was agitated thoroughly and the methylene chloride was removedby evaporation. The residue was heated for 45 minutes under nitrogen at285° C., whereupon there was obtained a linear polyarylate insoluble inmethylene chloride. Upon extraction of low molecular weight polymer withtetrahydrofuran, a high molecular weight material having a glasstransition temperature of 243° C. was obtained.

EXAMPLE 58

A mixture of 7.5 grams of a macrocyclic polyamide oligomer mixturesimilar to that of Example 20, 7.5 grams of caprolactam and 237 mg. (15mole percent based on caprolactam) of sodium hydride was heated in atest tube at 140° C. in a nitrogen atmosphere for 1 hour, during whichtime melting occurred and hydrogen was evolved. It was then heated for10 minutes at 265° C. and cooled. The solid product was removed bybreaking the test tube and a portion thereof was dissolved in chloroformand treated with trifluoroacetic anhydride, whereupon the polymerdissolved. Gel permeation chromatographic analysis of the solutionshowed the presence of a copolyamide having a number average molecularweight of 22,000 and a weight average molecular weight of 47,000.

EXAMPLE 59

A mixture of 1 gram of the crude macrocyclic polyamideimide oligomermixture of Example 40, 10 grams of caprolactam and 290 mg. of sodiumhydride was heated in a test tube at 150° C. in a nitrogen atmospherefor 1/2 hour, during which time melting occurred and hydrogen wasevolved. It was then heated for 12 minutes at 230° C. and cooled. Thesolid product was extracted with tetrahydrofuran, leaving as theinsoluble product a linear copolyamideimide having a weight averagemolecular weight of 27,000.

EXAMPLE 60

A 30% solids solution in dimethylacetamide of the substantiallylinear-free macrocyclic imide composition of Example 37 and 5 molepercent (based on structural units in said macrocyclic .[.polyimide.]..Iadd.imide.Iaddend.) of sodium sulfide was heated at 200° C. for 40minutes. Analysis of the resulting solution by gel permeationchromatography indicated the presence of a polymer having a numberaverage molecular weight of about 140,000, as well as low oligomers suchas the BPADA cyclic monoimide. The solution was spread on a glass plateand heated in vacuum at 160° C., yielding a polymer film of goodintegrity. The glass transition temperature of the polymer was 230° C.,identical to that of the extraction residue from Example 37.

EXAMPLE 61

The procedure of Example 60 was repeated, substituting lithium sulfidefor the sodium sulfide. A similar product was obtained after a somewhatlonger reaction time.

EXAMPLE 62

A mixture of 78 mg. of the substantially linear-free macrocyclic imidecomposition of Example 38, 0.023 ml. of a 0.02 M solution of the sodiumsalt of thiophenol in dimethylacetamide and 0.4 ml. of drydimethylacetamide was heated at 200° C. for about 1 hour, spread on aglass plate and heated in vacuum at 180° C. for an additional hour asthe solvent was evaporated. There was obtained a linear polyimide whichwas shown by gel permeation chromatography to have a number averagemolecular weight of about 20,000.

EXAMPLE 63

A toluene solution of 1 gram (1.9 mmol.) of the macrocyclicpolyethersulfone oligomer product of Example 45 and 5 mg. (0.02 mmol.)of the disodium salt of bisphenol A was distilled to remove the toluene.The vessel containing the residue was heated in a salt bath at 380°-400°C. for 15 minutes and cooled to room temperature. The solid product wasdissolved in chloroform and analyzed by high pressure liquidchromatography and gel permeation chromatography, which showed thepresence of linear polyethersulfone having a weight average molecularweight of about 80,000.

EXAMPLE 64

A solution of 26.7 mg. of the macrocyclic siloxane polyetherimidemonomer product of Example 42 and 1 microliter of methanesulfonic acidin 100 ml. of 1,2,4-trichlorobenzene was heated at 140° C. for one hour,with periodic analysis by gel permeation chromatography. After 40minutes, the weight average molecular weight relative to polystyrene wasabout 20,000 and no further increase was noted.

The solution was poured onto a glass plate and allowed to thickenovernight. It was then heated in a vacuum oven for 2 hours at 140° C.,yielding a clear, colorless film with excellent integrity. The film hada weight average molecular weight of about 200,000 and a glasstransition temperature of 109° C.

EXAMPLE 65

A mixture of 25 mg. of the macrocyclic siloxane polyetherimide monomerproduct of Example 42 and 1 microliter of methanesulfonic acid washeated for 10 minutes at 250° C., after which gel permeationchromatographic analysis showed a weight average molecular weightrelative to polystyrene of 26,200. The product was cooled, dissolved inchloroform and cast on a glass slide which was then heated for 1 hour at140° C., to produce a polymer film with a molecular weight of 39,800.

EXAMPLE 66

A solution of 600 mg. (0.68) mmol.) of the macrocyclic siloxanepolyetherimide of Example 44 and 8 mg. (0.06 mmol.) of sodiump-cresoxide in 1.8 ml. of o-dichlorobenzene was heated under reflux in anitrogen atmosphere for 4 hours, with stirring. The solution was cooledand poured slowly into 50 ml. of hexane, with stirring, and the solidpolymer which precipitated was filtered and dried. It had a weightaverage molecular weight relative to polystyrene of 15,000.

EXAMPLE 67

A solution of 130 mg. (0.15) mmol.) of the macrocyclic siloxanepolyetherimide of Example 44, 220 mg. (0.74 mmol.) ofoctamethylcyclotetrasiloxane and 2 microliters (0.02 mmol.) oftrifluoromethanesulfonic acid in 1.5 ml. of 12 freshly distilledchloroform was heated under nitrogen for hours at 60° C., with stirring.Upon analysis by gel permeation chromatography, the product was found tocomprise 80% by weight of a polyetherimide polysiloxane having a weightaverage molecular weight of 8,000.

What is claimed is:
 1. A composition comprising random macrocyclicmonomer and oligomer compounds corresponding to the formula ##STR20##wherein the Z¹ radicals are identical linking groups; A¹ is a spiro(bis)indane moiety of the formula ##STR21## about 60% of the R¹ groupsare divalent aromatic organic radicals and the balance thereof aredivalent aliphatic, alicyclic or aromatic organic radicals; each R² isindependently C₁₋₄ primary or secondary alkyl or halo; a is from 1 toabout 12, b is from 0 to 90% of total --A¹ --Z¹ --and --R¹ --Z¹--moieties and n is 0-3.
 2. A composition according to claim 1 wherein nis
 0. 3. A composition according to claim 1 wherein the compoundscontain at least one --R¹ --Z¹ --group.
 4. A composition according toclaim 3 wherein R¹ is ##STR22##
 5. A composition according to claim 1which comprises macrocyclic polyamides.
 6. A compositon according toclaim 5 which comprises structural units of the formula ##STR23##wherein: R⁴ is a substituted or unsubstituted C₂₋₄ alkylene, m-phenyleneor p-phenylene radical;R⁵ is a substituted or unsubstituted alkyleneradical or arylene radical other than o-arylene; and p is 0 or
 1. 7. Acomposition according to claim 6 wherein R⁵ is m-phenylene and p is 0.8. A composition according to claim 6 wherein R⁴ is m- or p-phenylene;R⁵ is A¹, m-phenylene, ##STR24## and p is
 1. .Iadd.
 9. A compositionaccording to claim 5 which comprises structural units of the formula##STR25##.Iaddend. wherein A⁴ is a monocyclic or bicyclic m- or p-linkedarylene radical or ##STR26## R³ is a divalent aliphatic or m- orp-linked monocyclic aromatic or alicyclic radical, and R⁶ is C₁₋₄primary or secondary alkyl, phenyl or substituted phenyl. .Iadd.
 10. Acomposition according to claim 9 wherein A⁴ is m-phenylene,##STR27##.Iaddend. has formula VIII wherein R³ is trimethylene and R⁶ ismethyl. .Iadd.
 11. A composition according to claim 5 wherein n is 0..Iaddend. .Iadd.12. A composition according to claim 1 which comprisesmacrocyclic polyimides. .Iaddend. .Iadd.13. A composition according toclaim 12 which comprises structural units of the formula##STR28##.Iaddend. wherein:Z² is a single bond, a divalent aliphatic oralicyclic radical containing about 1-12 carbon atoms, --O--, --CO--,--S--, --SO₂ --, --O--Q--O--, --SO₂ --Q--SO₂ --, ##STR29## Q is adivalent aliphatic or aromatic radical; R⁴ is a substituted orunsubstituted C₂₋₄ alkylene, m-phenylene or p-phenylene radical; R⁶ isC₁₋₄ primary or secondary alkyl, phenyl or substituted phenyl; and p is0 or
 1. .Iadd.14. A composition according to claim 13 wherein Z² is--S-- and p is
 0. .Iaddend. .Iadd.15. A composition according to claim13 wherein Z² is S, ##STR30## .Iaddend. R⁴ is p-phenylene and p is 1..Iadd.16. A composition according to claim 12 which comprises structuralunits of the formula ##STR31##.Iaddend. wherein:Z³ is R³, --R⁴ --Z⁴ --R⁴-- or ##STR32## Z⁴ is ##STR33## R³ is a divalent aliphatic or m- orp-linked monocyclic aromatic or alicyclic radical; R⁴ is a substitutedor unsubstituted C₂₋₄ alkylene, m-phenylene or p-phenylene radical; andR⁶ is C₁₋₄ primary or secondary alkyl, phenyl or substituted phenyl..Iadd.17. A composition according to claim 16 wherein Z³ is m-orp-phenylene, ##STR34## .Iaddend. .Iadd.18. A composition according toclaim 16 wherein n is
 0. .Iaddend. .Iadd.19. A composition according toclaim 1 which comprises macrocyclic polyetherketones orpolyethersulfones comprising structural units of the formula

    (XI) --O--A.sup.1 --O--A.sup.5 --,

wherein A⁵ is an aromatic radical containing at least one --CO-- or--SO₂ group. .Iaddend. .Iadd.20. A composition according to claim 19wherein A⁵ is ##STR35## .Iaddend. .Iadd.21. A composition according toclaim 19 wherein n is
 0. .Iaddend.